Pyrazoline derivatives

ABSTRACT

DIPHENYLPYRAZOLINE DERIVATIVES HAVING A 5-CARBOXYLIC ESTER OR AMIDE GROUP WHICH ARE USEFUL AS OPTICAL BRIGHTENERS FOR TEXTILE MATERIAL OF NATURAL OR SYNTHETIC FIBERS.

United States Patent US. Cl. 260-2393 4 Claims ABSTRACT OF THEDISCLOSURE Diphenylpyrazoline derivatives having a S-carboxylic ester oramide group which are useful as optical brighteners for textile materialof natural or synthetic fibers.

This invention relates to pyrazoline derivatives having the generalFormula I:

in which R denotes a hydrogen, chlorine or bromine atom, a methyl,methoxy, ethoxy, acetylamino, methylsulfonylamino or acetoxy group;

R denotes a hydrogen, chlorine or bromine atom or a methyl, ethyl,carboxyl, carboxylic ester, amide, N- substituted amide, nitrile,sulfonic acid, sulfonyl, sulfonic acid ester, sulfonamide orN-substituted sulfonamide group;

R denotes a hydrogen atom or a methyl, carboxylic ester,

amide or N-substituted amide group;

R denotes a hydrogen atom or a methyl group;

Y denotes a hydrogen or chlorine atom; and

X denotes a hydroxy, alkoxy, aralkoxy, aroxy, amino or N-substitutedamino group.

The radical R contains up to ten carbon atoms.

Examples of substituents R (other than those already mentioned are:carbomethoxy, carboethoxy, carbobutoxy, carbo-(B-hydroxy)-ethoxy,carbo-(fi-methoxy)-ethoxy, carbo-(5 acetoxy)-ethoxy,carbo-([i-chloro)-ethoxy, carbo (/3 dimethylamino) ethoxy, carbo (,8diethylamino) ethoxy, carbo (,B dibutylamino) ethoxy, carbo (5 hydroxy)propoxy, carbocyclohexyloxy, carbobenzyloxy, carbo 8 phenyl)-ethoxy,carbophenoxy, carbo (p chloro) phenoxy, carbo-(p-methyl)- phenoxy, carbo(p methoxy) phenoxy, N-methylamide, N-ethylamide, N-butylarnide,N-fi-hydroxyethylamide, N-B-chloroethylamide, N-fl-a-minoethylamide, N-

'y-methoxypropylamide, N-'y-dimethylaminopropylamide,

N-p-hydroxypropylamide, N-phenylamide, N,N-dimethylamide, N,Ndiethylamide, N,N di-(fl-hydroxy)-ethylamide, N methylN-fi-hydroxyethylamide, carboxylic piperidide, carboxylic morpholide,carboxylic piperazide, phenyl sulfonic esters, N-methylsulfonamide,N-ethylsulfonamide, N-butylsulfonamide, N B hydroxyethylsulfonamide, NB-chloroethylsulfonamide, N-fi-aminoethylsulfonamide, N 7methoxypropylsulfona-rnide, -N-'y-dimethylaminopropylsulfonamide, N 5hydroxypropylsulfonamide, N phenylsulfonamide, N,N dimethylsulfonamide,N,N-diethylsulfonamide, N,N-di-(B-hydroxyethyl) sulfonamide,N-methyl-N-fi-hydroxyethylsulfonamide, N-

methyl-N-phenylsulfonamide, sulfonic acid piperidide, sulfonic acidpiperazide, sulfonic acid morpholide, ethylsul- 3,753,978 Patented Aug.21, 1973 ice fonyl, B-methoxy-, B-ethoxy-, /8-butoxy-, B-dimethylaminoorfl-dibutylaminoethylsulfonyl.

Examples of R (in addition to hydrogen and methyl) are carbomethoxy,carboethoxy, carbobutoxy, carbophenoxy and the amide radicals specifiedfor R The total number of carbon atoms in the radicals X is up to 10.

Examples of X (in addition to hydroxy) are:

industrially have the General Formula II:

in which R denotes a hydrogen atom or a carboxylic ester, amide,N-substituted amide, sulfonic acid, alkylsulfonyl, sulfonamide orN-substituted sulfonamide group and R and X have the meanings givenabove. Particularly suitable N-substituted amide and sulfonamide groupsare N-monosubstituted or N,N-di-substituted amide and sulufonamidegroups.

Of these substances, those compounds are preferred in which R denotes asulfonic acid or a sulfonamide group (including a N-substitutedsulfonamide group).

Examples of preferred radicals X are: alkoxy radicals having one to fourcarbon atoms or radicals derived from aliphatic amines and having atotal of one to eight carbon atoms.

R (111 an unsaturated compound having the general Formula IV:

C=C/ R ("J-X Ir) Production of nitrilimines and adding on theunsaturated compound are described for example in Tetrahedron 17 (1962),3.

Compounds having the Formula V:

o 3 R R v \C=C/ m (Z-X 1 0 may also be reacted with phenylhydrazinehaving the Formula VI:

NNH2 This reaction may be carried out particularly smoothly by adding onhydrogen halide to compounds having the Formula V in which X denotes OHand then allowing phenylhydrazines having the Formula VI to act thereon.

By adding on hydrogen halide, preefrably as a gas in glacial acetic acidor propionic acid, compounds having the general Formula VII:

0 (VII) in which Hal denotes a chlorine or bromine atom are obtainedfrom carboxylic acids having the Formula V.

After the compounds having the Formula VII have been reacted with thephenylhydrazines, the radical X may be introduced by conventionalmethods.

It is also possible to use the corresponding esters in the reaction withhydrogen halide instead of the carboxylic acids (X=OH).

Reaction of the Components VI and VII is advantageously carried out insolvents such as water, glacial acetic acid, propionic acid, methanol,ethanol, glycol, methylglycol, dimethylformamide, acetonitrile orN-methylpyrrolidone. The components may be reacted with each other inthe solvent at a temperature of from 0 to 120 C., preferably from 40 to80 C. The reaction period is as a rule from one to ten hours.

'When R denotes a sulfonic ester or sulfonamide group it is advantageousto introduce this radical into the compounds having the formula:

by sulfochlorination, i.e. by way of a sulfochloride group.

The invention is illustrated by the following examples. Unless statedotherwise, parts and percentages in the examples are by weight.

EXAMPLE 1 -c 0 0 CH3 EXAMPLE 2 130 parts ofbenzaldehyde-a-chloro-p-dimethylaminosulfonylphenylhydrazone isdispersed in 2000 parts of toluene and of acrylamide is added. 121 partsof triethylamine is allowed to flow in within five minutes and the Wholeis heated for five hours at 80 C. The greater part of the solvent isthen removed under subatmospheric pressure, the residue is suctionfiltered and treated at 20 C. with 500 parts of Water to removetriethylamine hydrochloride. Another suction filtration gives 104 partsof 1- (p-dimethylaminosulfonylphenyl) 3 phenylpyrazoline- A -S-amide(melting point 232 to 235) having the formula:

N -(1 ON H2 EXAMPLE 3 20 parts of1-(p-dimethylaminosulfonylphenyl)-3-(pchlorophenyl) pyrazoline A 5carboxylic methyl ester in 60 parts of N,N-dimethyl-1,3-diaminopropanehas 0.1 part of sodium methylate added to it and the whole is heated forthree hours at 80 C. The reaction product is precipitated with 300 partsof water. 18.5 parts of '1.-(pdimethylarninosulfonylphenyl) 3 (pchlorophenyl)- pyrazoline-A -5-carboxylic (v N,Ndimethylaminopropyl)amide having the melting point 138 to 140 C. isobtained which has the formula:

40 parts of 1-(pN-methyl-N-phenylaminosulfonyl)-phenyl)-3-phenylpyraz0line-A -5-carboxylic methyl ester and 0.1 part ofsodium methylate are heated for four hours at 80 C. in parts ofethanolamine. The reaction solution is then poured into 500 parts ofwater and the de posited precipitate is suction filtered and Washed withSOgNiCHa):

water. 42 parts of1-(p-N-methyl-N-phenylaminosulfonyl)-phenyl-3-phenylpyrazoline A 5carboxylic-fi-hydroxyethylamide having a melting point of 191 to 193 Cis obtained which has the formula:

N H-C Hg 0 H OH EXAMPLE 5 41 parts of o,p-dichlorobenzaldehyde achloro-p-(dimethylaminosulfonyl) phenylhydrazone, 0.1 part ofhydroquinone and 27 parts of fi-chloroethyl acrylate aredissolved in 300parts of toluene at 90 C. Then within five minutes 20 parts oftriethylamine is allowed to flow in and the whole is heated for anothertwenty minutes at 90 C. The reaction mixture is externally cooled withice-water and the deposited precipitate is suction filtered. Theprecipitate is then stirred with 200 parts of Water and again filteredwith suction. 40 parts of 1- (p-dimethylaminosulfonylphenyl) 3'(o,p-dichlorophenyl)pyrazoline-A 5-carboxylic-B-chloroethyl ester havinga melting point of 152 to 154 C. is obtained which has the formula:

wsozmcnm COOCHzCHzCl Another 6 parts of the compound is recovered byconcentrating the toluene solution and grinding it with 2 parts ofmethanol.

EXAMPLE 6 50 parts of p-chlorobenzaldehyde-u-chloro-p'-(morpholinosulfonyl)-phenylhydrazone, 0.3 part of hydroquinone and '27parts of allyl acrylate are heated to 90 C. Then within five minutes 24parts of triethylamine is allowed to flow in and the reaction mixture isstirred at 90 C. for another twenty minutes and cooled. The depositedtriethylamine hydrochloride is suction filtered and the filtrate isconcentrated at subatmospheric pressure to one quarter of its originalvolume. 48 parts of l-(p' morpholinosulfonylphenyl) 3 (pchlorophenyl)-pyrazoline-A -5-carboxylic allyl ester having the meltingpoint 126 to 129 C. is'obtained by suction filtration; it has theformula:

\NGSOZ-N/W COOCH2OH=CHI EXAMPLE 7 100 parts of 1-(p-morpholinosulfonylphenyl) 3 (p'- chlorophenyl)pyrazoline-A-5-carboxylic methyl ester, 0.5 part of p-toluenesulfonic acid and 150parts of N,N-diethyl-B-aminoethanol are dissolved in 250 parts ofdimethylformamide at 120 C. The reaction mixture is then kept at thistemperature for twelve hours, a weak stream of nitrogen being passedthrough the apparatus so that the methanol formed is removed. Themixture is then cooled to 60 to 80 C. and poured into a solution of 65parts of glacial acetic acid in 4000 parts of water. After the whole hasbeen stirred for twenty minutes the precipitate is suction filtered andwashed with 1000 parts of water. 92 parts of1-(p-morpholinosulfonylphenyl)-3-(p'-chlorophenyl)-pyrazo]ineA-5-carboXylic (B N,N diethylaminoethyl) ester having a melting point of102 to 105 C. is obtained; it has the formula:

EXAMPLE 8 100 parts of 1-(p-morpholinosulfonylphenyl) 3 (p'chlorophenyl)-pyrazoline-A -5-carboxylic methyl ester, 0.5 part ofsodium methylate and 150 parts of.1,2-diaminoethane are introduced into2500 parts of toluene at 90 C. A weak stream of nitrogen is passedthrough the solution which is heated for ten hours at 90 C. It is thencooled with ice-Water and the deposited precipitate is suction filteredand washed with 30 parts of methanol. 90 parts of 1(p-morpholinosulfonylphenyl)-3-(p'-chlorophenyl)- A-5-carboxylic-(B-aminoethyl)-amide having a melting point of 214 to 216C. is obtained which has the formula:

EXAMPLE 9 and 78.6 parts of methyl acrylate are heated to C. in 900parts of toluene to dissolve them. 92.4 parts of .triethylamine isallowed to fiow in within five minutes and heating at 80 C. is continuedfor another two hours and at C. for another thirty minutesHIhe cooledreaction mixture is freed from precipitated triethylamine hydro-vchloride by suction filtration and the filtrate is concentrated atsubatmospheric pressure. The residue is: stirred with 70 parts ofmethanol at 0 C. On suction filtration, 146 parts of1-(p-carbethoxyphenyl)-3-(p-chlorophenyl)- pyrazoline-A -5-carboxylicmethyl ester is obtained having a melting point of 137 to 139 C.; it hasthe formula;

EXAMPLE 10 26 parts of p-ch1orobenzaldehyde a. ChlOIO-(Prcar-bethoxyphenyl)-hydrazone, 0.2 part of hydroquinone and 16 parts ofallyl acrylate are dissolved inparts .of toluene at 90 C. 12 parts oftriethylamine is allowed EXAMPLE 11 20 parts of 1 (p' carbethoxyphenyl)3 -(p-chlorophenyl) pyrazoline A 5 carboxylic methyl ester, 50 parts ofN-methylpyrrolidone-2, 30 parts of diethylamine and 0.1 part of sodiummethylate are heatedina 250- cm. agitated autoclave for twenty-fourhours at 140 C:. After it has cooled, suction filtration is carried out,and the filtrate is stirred into 300 parts of Water at 20 C., againsuction filtered and dried. 17 parts of l-(p' carbodiethylaminophenyl) 3(p-chlorophenyl) pyrazoline- A 5 carboxylic diethylamide (melting point176 .to 178 C.) is obtained having the formula:

N CIQT NGCOMOJ -CON(CH i EXAMPLE 12 37 parts of p chlorobenzaldehyde orchloro-p-(N, N dimethylaminosulfonyl) phenylhydrazone and 28 parts ofdimethyl maleate are suspended in 750 parts of toluene at 60 C. and then20 parts of triethylamine is allowed to flow in within five minutes.After fifteen minutes at 60 C., the whole has passed into solution. Itis heated at 60 C. for another four hours, then cooled and thetriethylamine hydrochloride suction filtered; The filtrate isconcentrated at sub-atmospheric pressure and the residue stirred with 10parts of methanoL'After suction filtration, 27 parts of 1 (p N,Ndimethylaminosulfonylphenyl) 3 (p' chlorophenyl) pyrazolineis obtainedwhich after having been recrystallized from acetonitrile has a meltingpoint of 156 to 158 C.

The 8-(4-chlorobenzoyl)-a-chloropropionic acid used is prepared asfollows:

210 parts of p-chlorobenzoylacrylic acid is suspended in 800 parts ofglacial acetic acid. 100 parts of hydrogen chloride is passed into thissuspension at 10 to 20; the yellow color disappears and solution takesplace. The whole is stirred for two hours at 20 C., 3000 parts of wateris added and the product is suction filtered and dried. 230 parts of)3-(4-chlorobenz0yl)-a-chloropropionic acid is obtained having a meltingpoint of 127 to 130 C. It has the following structure:

01--o-om-ou-o OH EXAMPLE 88 H i H and a melting point of 163 to 167 C.After having been recrystallized from acetonitrile, the compound meltsat 170 to 173 C.

EXAMPLE 89- 13 parts of 1,3-bis-p-chlorophenyl-M-pyrazoline-S-carboxylicacid is boiled under reflux with 80 parts of methanol and 0.5 part ofconcentrated sulfuric acid for 3 hours. The cold reaction mixture issuction filtered and washed with water. 10 parts of1,3-bis-p-chlorophenyl- M-pyrazoline-S-carboxylic methyl ester isobtained having a melting point of 117 to 119 C. and the structure:

-C 00 C H:

EXAMPLE 90 25 parts of 13-(4-chlorobenzoyl)-a-chloropropionic acid, 25parts of p-tolylhydrazine sulfate and 10 parts of sodium carbonate(anhydrous) in 400 parts of water are stirred for four hours at 50 C.The whole is then cooled to 20 C. After suction filtration, washing with200 parts of water and drying, 29 parts of1-(p-tolyl)-3-p'-chlorophenyl)A pyrazoline-S-carboxylic acid is obtainedhaving the melting point 202 to 205 C. and the structure:

H OOH EXAMPLE 91 20 parts of (4-chlorobenzoyl)-a-chloropropionic acidand 24 parts of p-hydrazinobenzoic acid in 150 parts of glacial aceticacid are heated to 55 C. 250 parts of water is added to the hot solutionwhich is cooled to 20 C. The deposited product is suction filtered,Washed with 300 parts of water and dried. 25 parts of l-p-carboxyphenyl-3-p'-chlorophenyl-A -pyrazolinc-S-carboxylic acid is ob- 12 tained whichhas a melting point of 273 to 276 C. and the structure:

C O O H EXAMPLE 92 6 parts of 1-phenyl-3-p-chlorophenyl-A -pyraZOline-S-carboxylic methyl ester is introduced in portions at 10 to 20 C. into 30parts of chlorosulfonic acid and stirred for two hours at 20 C. Thesulfochloride formed is precipitated with 200 parts of ice-water,suction filtered and dissolved while moist in 50 parts of chloroform. 17parts of morpholine is added and the whole is boiled under reflux fortwo hours. The solvent is then distilled 01f and the residue is washedwith parts of water and dried. 5 parts of1-p-morpholinosulfonylphenyl-3-p-chloropheny1-A -pyrazoline-5-carboxylicmethyl ester is obtained having the structure:

N 1: H H

A OOCH:

After recrystallization from acetonitrile, it has a melting point of 202to 206 C.

The pyrazoline carboxylic ester is prepared from the pyrazolinecarboxylic acid (Example 87) in a manner analogous to Example 89. Theester has a melting point of to 107 C.

EXAMPLE 93 25 parts of B-(4-chlorobenzoyl)-u-chloropropionic acid, 28parts of p-hydrazinobenzenesulfonic morpholide and 8 parts of sodiumacetate in 150 parts of glacial acetic acid are stirred for one hour at20 C. and for two hours at 55 C. 300 parts of water is added and thewhole is allowed to cool to 20 C., filtered, washed with 150 parts ofwater, dried and 41 parts of '1-(p-morpholinosulfonylphenyl)-3-(p'-chlorophenyl)-A -pyrazoline-S-carboxylic acid is obtained. The acidis dissolved in 240 parts of methanol, 1 part of concentrated sulfuricacid is added and the Whole is boiled .for seven hours under reflux. Thesolvent is distilled 01f and the residue is washed with water and dried.37 parts of the carboxylic methyl ester having the formula:

COOCH:

is obtained which after having been recrystallized from acetonitrilemelts at 204 to 206 C. and is identical with the product obtained inExample 92.

EXAMPLE 94 40 parts of 1-p-dimethylaminosulfonylphenyl-3-p'-chlorophenylA pyrazoline-S-carboxylic methyl ester, 0.1 part of sodium methylate andparts of 1,2-diaminoethane are heated for six hours at 80 C. undernitrogen. The whole is allowed to cool and is stirred into 250 parts ofwater so that the product crystallizes. 38 parts of'amide is obtainedhaving the melting point 208 to 211 C. and the structure:

terification of the pyrazoline-carboxylic acid formed, or bysulfochlorination and aminolysis ofl-phenyl-3-p-chlorophenylpyrazoline-S-carboxylic ester-analogousto-Example EXAMPLE 95 H/--H H CONH(CH2)aN(CHs)2 EXAMPLE 96 35 parts ofhydrogen chloride is passed at to 20 C. into a solution of 27 parts ofp-mesylaminobenzoylacrylic acid having the formula:

in 130 parts of glacial acetic acid and the whole is allowed to standovernight. 21 parts of 18-4-methylsulfonylamin0-benzoyl)-a-chl0ropropionic acid is precipitated having a melting pointof 178 to 182 C. and the formula:

14 15 parts of this compound is dissolved hot in 100 parts of glacialacetic acid, 10 parts of" phenylhydrazine is addedandthe whole .isstirred for two hours at C.

200 parts of water is then allowed to how in,- stirring is continued forthirty minutes and the precipitate is filtered and washed with parts ofwater. 18 parts of l-phenyl- 3 (p methylsulfonylaminophenyl) Apyrazoline5- carboxylic acid is obtained having a melting point of'193to 196 C. and the formula:

N CHaSOiNHQT coon EXA'MPLE 97 20 parts of phenylhydrazine-4-sulfonicacid and 9 parts of sodium hydrogen carbonate are dissolved in ZOO-partsof hot water. Then 25 parts of B-(4-chl0robenzoyl) -achloropropionicacid is introduced into this solution at 70 C. The whole is stirred .foranother 2 /2 hours at 70 C., 70 parts of sodium chloride is added, andthe whole is cooled to 15 C. and suction filtered.

37 parts of the compound having the formula:

is obtained.

The compounds identified in the following table by indicating theirsubstituents may be obtained by methods analogous to those described inExamples 87 to 97:

. CHQSOB-NH-G- -CHPCEFC OOH Example R R1 X 92 H 4-SO3Na NH (CH:)z-N H 99H 3-S0aNa nncnga-mmm), 10o H 4-01 oH,

N omr-N 101.; c1 4-OH: Nn-cmomosotn 102 o1 1 Y o-cmomosotn- SOi-N N--CHa4-01 OCH CHgN(CHa)g 4-01 O-CHzCfia-N (04 b):

4-SO Na ocH-oH1-N cm 106..:.-:7..- CH O-C H 4-SO1'N o '7 107-.:-:.:-:;.CH: 4-01 0CH|C|H5 10s OCH o-c H 8 4-so1N H 5 109-.--: OCH! 450300 15O-CHCHa-IKCHfig 110 OCaHs 4-CN NH-(CH1) -N(C:Hs)z 111 CHaCONH 4-CONH1NH-(CHDa-NKJHQ; 112 CHSCONH 3-SOaNa OCHICH|N(C1HA):

in which R is hydrogen, chlorine, bromine or methyl, R

SO NHC H alkyLthe alkyl'group having 1 to 4 carbon atoms,

R is hydrogen or methyl, X is hydroxy, alkoxy of 1 to 8 carbon atoms,fl-hydroxyethoxy, B-hydroxypropoxy,

methoxyethoxy, ,fl-chloroethoxy, ,B-acetoxyethoxy, allyloxy,cyclohexyloxy,.benzyloxy, B-phenylethoxy, phenoxy, phenoxysubstituted'by chlorine, methyl or methoxy, fl-

drogen or chlorine,

(B-methoxyethoxy)-ethoxy, or fi-sulfoethoxy and Y is hy- TABLE'ContinuedExample R R! X 113 0 4-SD2NHC4H9 NH-CHzCHrNHSOaH CHzC m 0 0-oHcH,'-oso,H

' 4-S0='N NCH:

CHaC\ 0 4 COOC2H OCH;GHN(C4H;),

0:04:35 2)aN(C a)2 SO:UH2C 2OCHa 0GH2CH2N(C1H5)2 SO CHaCHiOCLHi 0C aS02CHzCH:N(CHa)I NH(CH1)3N(CH3)| SO:CH2CH2N(C4H1))2 OCH;SO:CHQCHQNH(CH2)3N(CH3)I OCH SOzCHnCHzO CHICH2N (C2115)! OCIHBS05CH1CH;0(IJHCH1N(CH:;): OCH; CH3

We claim: 2. A pyrazoline as claimed in claim 1 wherein R is sul- 1. Apyrazoline having the formula fcnamide or N-monoorN,N-dialkyl-substituted sulfonic acid amide, said alkyl groups having 1to 4 carbon atoms,

N-monoor N,N-dihydroxyalkyl substituted sulfonic acid amide, saidhydroxyalkyl groups having 2 or 3 carbon atoms, N,N-dialkylaminopropylsulfonic acid amides, said alkyl groups having 1 to 4 carbon atoms orone of the radicals -SO NHC H Cl, .SO NHC H NH --SO NHC H O alkyl, thealkyl group having 1 to 4 carbon atoms,

S0N N-CH;

References Cited UNITED STATES PATENTS 12/1971 Krause et a1 260239.9

HENRY R. JILES, Primary Examiner C. M. S, JA I SLE, Assistant ExaminerUS. Cl. X.R.

v UNITED STATES swam mmw mmmm UK? mmaiw Inventofls) It: is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown' below:

001mm 2, lins 65 "sulufsnamide" shcvuld read msulfonamide M Column 3,line 37,, preefrably shculci read M preferably Columns 9 i9; 10; EXsle80; column "33",; inssrt- H 0 shcmld read I Column 12, line "(3"analogous 139'" should read analogously 8011mm 15, line 41"SOENHCZI-MCMI," 'shduld read as SOQNHCZHACI Signed and sealed this I19th day of November 1974-.

(SEAL) Attest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents mm PO-1050 (10-69) UscoMM-DC eoames I 9 LS. GOVERNMENT PRINTINGDFHCE 19H 0-356-33.

